Stabilized trichloroethylene or tetrachloroethylene

ABSTRACT

Trichloroethylene or tetrachloroethylene stabilized against decomposition by heat, light, air, moisture and metals, said trichloroethylene and tetrachloroethylene containing A. GLYCERIN OR GLYCIDOL; B. AT LEAST ONE PHENOLIC DERIVATIVE SELECTED FROM THE GROUP CONSISTING OF P-METHOXYPHENOL, 2,6-DITERT-BUTYL-4-METHYLPHENOL, P-TERT-BUTYLPHENOL, P-SEC-BUTYLPHENOL AND THYMOL; C. DIISOPROPYLAMINE; AND D. EPICHLOROHYDRIN OR BUTYLENE OXIDE.

States Patent 11 1 1111 3,85,367 Katsm'amgawa et a1. Dec. 3, 1974 [54] STABHLIZED TRICHLOROETHYLENE 0R 2,981,760 4/1961 Ferri et a1. 260/6525 R TETRACHLOROETHYLENE 3,043,888 7/1962 Pray et a1 3,133,885 5/1964 Petering et al 260/6525 R Inventors: Seiichi tsu agfl a; Norihisa 3,152,191 10/1964 Cormany et a1. 260/6525 R Koketsu, both of Saitama-ken, 3,188,355 6/1965 Petering 260/6525 R Japan 3,293,312 12/1966 Ryckaert et a1 260/6525 R 2 3,676,507 7/1972 Campbell et a1 260/6525 R [73] Ass1gnee: Central Glass (10., Ltd., Yamaguchl'ken Japan Primary Examinerl-I0ward T. Mars [22] Filed: Dec. 21, 1971 Attorney, Agent, or Firm-Sherman & Shalloway [21] Appl. No; 210,576

[57] ABSTRACT [30] Foreign Applicafiun Priority Data 1 Tric 'hloroethylene or tetrachlo roethy lene sitabilized agamst decomposmon by heat, l1ght, a1r,mo1sture and 1970 Japan 45415687 metals, said trichloroethylene and tetrachloroethylene containing [52] US. Cl. 260/6525 R, 252/171 glycerin or glycidol; [51] 1111. C1. C07C 17/40, C076 17/42 at least one phenglic derivative selected from the [58] lFielu'lof Search 260/652.5; 252/171 group Consisting of p methoxyphenoh 2,6-ditert-butyl-4-methylpheno1, [56] References cued p-tert-butylphenol, p-sec-butylphenol and thymol;

UNITED STATES PATENTS 2,371,644 3/1945 Petering Ct 211 260/6525 ux ii 'pr pyl mi n 2,906,782 9/1959 Ferri e1 a1. 260/6525 R d. epichlorohydrin or butylene oxide. 2,935,537 5/1960 Daras 260/6525 R 4/1961 Daras 260/6525 R 1 Clam, N0 Drawmgs l STABllLlZED TRICHLOROETHYLENE on TETRACHLOROETHYLENE BACKGROUND OF THE INVENTION This invention relates to trichloroethylene or tetrachloroethylene, which has been stabilized against decomposition by heat, light, air, moisture and metals.

Since trichloroethylene and tetrachloroethylene possess degreasing power, they are widely used as a degreaser of metallic products or for dry cleaning of textile fabrics to exhibit good extraction of oils and fats. However, trichloroethylene and tetrachloroethylene, being susceptible to decomposition by the action of such as heat, light, air, moisture and metals, tend to form such acid products as dichloroacetic acid or hydrochloric acid, as well as such toxic products as phosgene and tarry substances. In'consequence, serious difficulties are encountered at times in the storage, transportation, use and recovery of trichloroethylene and tetrach1oroethylene.

When trichloroethylene or tetrachloroethylene containing such decomposing products as'hydrochloric acid even in a small quantity is used as a cleaning agent for practical purposes, metals are often corroded and not only difficult technologically but economically as well. Commercially produced trichloroethylene or tetrachloroethyleneare usually susceptible to decomposition by heat, light, air, moisture and metals.

For preventing such a decomposition, the practice heretofore was to stabilize the trichlorethylene or tetrachloroethylene by adding singly or in combination such compounds as, for example, the phenols, aliphatic epoxides, alcohols, amines and aliphatic nitriles. However, it frequently happened that the trichloroethylene or tetrachloroethylene containing these stabilizing compounds in a suitable amount did not have a satisfactory stability when used under relatively harsh conditions. This happened because of the infinite variety of the users cleaning conditions (e.g. differences in the type of cleaning machine used, method of heating, class of oil, amount of moisture content, the article to be cleansed, etc.) and hence difficulty was experienced in obtaining a stability in which all the cleansing conditions were completely-surmounted. I

SUMMARY OFTHE INVENTION The present invention provides a stabilized trichloroethylene. ortetrachloroethylene containing a. glycerin or glycidol; b. at least onephenolic derivative selected from the group consisting of p-methoxyphenol, 2,6-ditertbutyl-4-methylphenol, -p-tert-butylphenol, p-sec- The stabilized trichloroethylene or tetrachloroethylene composition of the present invention contains the four components in the ranges hereinabove indicated, and, as a result, possesses an excellent stability 'to decomposition by heat, light, air, moisture and metals.

1 Trichloroethylene or tetrachloroethylene containing the aforesaid four components in an amount less than the foregoing ranges does not possess a satisfactory stability. On the other hand, trichloroethylene or tetrachloroethylene containing the aforesaid four components in amounts exceeding the foregoing limits does not have any increased stability.' Again, addition in such large amounts would not be an advantage economically.

Trichloroethylene or tetrachloroethylene. which does not contain at least one of each of the aforesaid four components does notpossess a satisfactory stability to decomposition by heat, light, air, moisture and metals.

Any'of the customaiy procedures may be employed in adding the aforesaid four components to the trichlo roethylene or tetrachloroethylene. The four components may be added in any sequence or may be added at the same time. The addition is preferably carried out with stirring at normal atmospheric pressure and ambient temperature.

In the following experiments the determination of the stability was made by means of the iron piece dipping corrosion test, a test in accordance with the Method of Testing Trichloroethylene (JIS K 1508 standards), and theStabilization Test of Perchloroethylene in accordance with the standards of the National Institute of Dry Cleaners (hereinafter referred to asthe NID Standard Test). These three testing methods were found to be tests that were necessary as a result of having made comparisons with the stability tests of the cleaning solvent in the various practical cleaning methods. A high degree of stability is guaranteed only in the case of the trichlorethylene or tetrachloroethylene which demonstrates good results in all three of these tests.

' EXAMPLES 1. Iron piece dipping corrosion test. A soft iron piece [dimensions 0.5mm (thickness) X 13 mm X50 mm] whose surface has been lusteredby polishing is dipped intrichloroethylene or'tetrachloroethylene containing the prescribed stabilizers andleft standing for a given period of time at room tempera ture. Then the state of corrosion of the soft iron piece is observed with the naked eye.

2. Test in accordance with the J lS K 1 508 standards.

Two hundred milliliters of trichloroethylene or'tetrachloroethylene containing the prescribed stabilizers is charged to a 500 ml flask equipped with a reflux consuspended in the vapor phase. This is followed by introducing water-saturated oxygen into the sample liquid at the rate of 10 12 bubblesper minute while heating the bottom of the flask by irradiation with a l50-W electric lamp. After continuing the heating and the introduction of the oxygen for 48 hours, the sample liquid is cooled to room temperature, and the conditions of the soft iron pieces and the sample liquid are observed. Further, the pH of the sample liquid is then determined in the following manner for ascertaining the extent of its decomposition. Fifty milliliter of the sample liquid and 50 milliliter of pure water of pH 6.5 are placed in a 100-ml separating funnel and shaken vigorously for 2 minutes. The pH of the water layer is then measured and this is compared with the similarly obtained pH of the sample liquid before its use in the foregoing test.

One hundred milliliters of trichloroethylene or tetrachloroethylene containing the prescribed stabilizersare placed in a 300-ml flask, after which a copper piece [dimensions of 0.55 mm (thickness) X 20 mm X 75 mm] whose surface has been lustered by polishing is placed in the flask. Next, after adding 0.5 milliliter of water, a Soxhlet extractor is attached and a similar copper piece is placed therein. Further, above the Soxhlet extractor is attached a valve type condenser, and in the lower end thereof there is suspended a similar copper piece. So as to effect the condensation of the foregoing copper pieces of the trichloroethylene or tetrachloroethylene by evaporation, the bottom of the flask is heated by means of a heater. On the other hand, irradiation by means of a 100-W electric lamp disposed at a point 2.5 centimeters from the Soxhlet extractor is carried out for effecting the oxidation by exposure to light.

After continuing the foregoing test for 48 hours, the total weight loss of the copper pieces and the increase in the acid component in the sample liquids, as measured by the same procedure as in test (2), are determined. V

The results obtained in the foregoing'tests, (l), (2)

3. Test in accordance with the MD standard test. 25 and (3) are Shown i h f llowing t bl Table RESULTS OF STABILITY TESTS OF TRICHLOROETHYLENEAND TETRACI-TLOROETHYLENE Exp- eri- TCE Stabilizer ment or No. PCE GCE GCD PMP BHT PBP PSBP TM DIPA ECH BO Others I TCE 2 do. 0001 3 do. do. 0.1 4 do, do. 0.0l2 5 do. do. do. 0.] 6 PCE do. do. TEA 0.02 7 TCE 1 do. 8 do. 0.001 0.01 r 9 ,do. 0.01 0.012 0.1 n- 0.2

BuOH- 10 do. do. do. 1 STA 0.01

11 do. 0.] 0.001 do DAA 0.018 12 PCE 0.01 do. do. DEA 0.02 13 TCE 0.1 do. TEA 0.007 14 do. do. do. MH 0.017 15 do. 0.01 0.01 0.004 [PA 0.005 16 I do. 0.1 a 0.02. 0.012 l7 TCE (commercial product) l8 PCE 0.1 0.001 0.012 0.1 19 TCE 0.01 do. do. do. 20 PCE do. do. do. 21 TCE 0.1 do. do. do. water content 100 ppm. 22 PCE 0.01 0.01 do. do. water saturated 23 do. do. 0.1 do. do. 24 TCE 0.1 0.002 do. do.

25 do. do. 0.002 do. do. 26 do. do. 0.001 0.01 0.2 27 PCE do. 0.002 n 0.02 0.1 28 TCE 0.01 0.001 0.001 0.01 0.1

TCE trichloroethylene PCE tetrachloroethylene GOE glycerin GCD glycidol PMP p-methoxyphenol BHT ZJSQdi-tert.-butyl-4-methylphenol PBP p-terL-butylphenol I PSBP: p'see-butylphenol I TM :-thymol I D1PA diisopmpylamine ECH epichlorohydrin BO': butylene oxide TEA triethylarnine n-BuOH: n-butanol STA stearylamine DAA diarylamine DEA diethanolamine MH morpholine IPA isopropylamine Test in Accordance with .TIS Test in Accordance with NID Imn Piece K4503 S'llgrjard Test for 10E Standard Te t for PGE Dipping Iron Iron Change Copper 01 Loss Change Liquid Piece Piece in B in- 11 Liquid ggggz gfigz Piece in of Copper in :H ggg phase in Vapor Phase Va r Piece B9- 116610 Phase fore After Llquld SW11 P (2%) fm After (mm 0.) rusting mating t l of whole of whole 6.5 1.8 brown o o corroded 21.6 6.5 5.8' appears surface surface I er 2 days 2 6 6.5 2.0 0 6 0 Partly 4.2 6.5 6.1.

corrcded r r K light Z. 0 0 Q o 10.6 9.9 yellow 0 0 .0 1.5 13.0 10.0

r rust appears 5 o 0 o 9.0 9.8 o 0 0 o 3.0 9.6 9.0 after 3 days light partly 4 6 0 o o 9.3 9.1 yellow 0 0 corroded .2 9.3 9.3

rusting rusting 7 0 of whole of whole 6.5 2.1 0 o 0 2.6 6.5 6.1. a i g surface surface r a er l i no rusting E. o 0.5 2.0 0 c 0 0.0 6.5 6.3 after 20 days 0 mat appears 9 6 6 6 10.1 10.1 o o o O after 3 ays 1 rusting. rusting t 10 6 01' 6661 or 611616 6.5 2.1 6116.. 6 6 I 6 7.0 6.5 5.7 g gf surface surface v er ys light n0 rusting 11 yen-w o o 9.1 9.2 yellow no luster o o 0.0 9.1 8.7 after 7 y Y u 1 l3 ish o 0 0.9 8.0 c 0 0 3.4 8.9 8.8 n

1!. c 0 o 8.8 8.7 Y corroded izzi i izzi g 2.6 8.8 8.6-

ting rusting light ms llght partly partly 15 of whole of whole 9. 1.8 0 4.0 9.4 6.9

yellow surface Surface yellow corroded corroded yellowno rusting l6 0 o o 10.0 10.0 ish o o o 0.1 10.0 10.0 after l days small amount 17 O O 6 10.6 10.6 61166 0' O Biggi 1.5 10.6 10.6 6r black rust after 3 days no lusting 18 o o 0 10.0 10.0 o o 0 o 0.4 10.0 10.0 after 30 a 19 O 6 O 10.-1. 10.1 6 O 6 6 1.2 10.1 10.1

20 o o o 4 9.8 9.8 0 o o c 1.8 9.8 9.8

- 1 after days 22 o 0 0 9.8 9.8 0 0 o o 1.3 9. 9.

21. 0 0 Y o 9.5 9.5 0 0 0 o 1.6 9.5 9.6

25.! O. 1 0 .0 9.4 9.1. O o 0 0 0.1 9.1. 9.1. 26 6 '6 6"-'9.1 9.0 O Y 6 6 -6 1.0 0.1.9.1

' ieg'in 1158mm ""te iditifki s Test in Accordan C with I K-1 08 Sandal-d Test for NE Saandard Test for PCE P me N Change Co co er Copper Wt Loss Change Tippm? Liquid Piece Piece in in pa Liquid Piece in of Copper in pH rr slon Plece 1n llece 1n Test Phase in Vapor Be- After Phase Li uid Soxhlet Va or Plece Be- Aft Linuid Phase fore q Plw (1 g) fore er (mom 2'7 0 0 o 10.4 10.1,, o o o 0 5.6 10.4 10.4

28' o o D 952' 9.2 o o o o 0.0 9.2 9.2

Note l) o No change.

2) Experiment Nos. 1 17 are Controls and Experiment lbs. 13 28 are Examples of this invention.

lt is from foregoing tables that the trichloroethylene or tetrachloroethylene containing the fourcomponents of the invention demonstrate excellent results in all three tests: the test in accordance with MS K-1508 standard test, the test in accordance with the MD standard test, and the iron'piece dipping corrosion test; ofitfie'otherhand, it is seen that in the caseof tri chloroethylene or tetrachloroethylene which does not contain at least one of each of the four components or in the case of thecomrnercially available prod uct, unsatisfactory results are obtained in one or more of the foregoing three classes of tests.

and d. 0.001 to 1.0 weight percent of epichlorohydrin. 

1. A STABILIZED COMPOSITION CONSISTING ESSENTIALLY OF TRICHLOROETHYLENE OR TETRACHLORETHYLENE AND A. 0.0001 TO 1.0 WEIGHT PERCENT OF GLYCERIN; B. 0.00001 TO 0.1 WEIGHT PERCENT OF AT LEAST ONE PHENOLIC DERIVATIVE SELECTED FROM THE GROUP CONSISTING OF PMETHOXYPHENOL, 2,6-DI-TERT.-BUTYL-4-METHYPHENOL, PTERT-BUTYLPHENOL, P-SEC-BUTYL-PHENOL AND TRYMOL; C. 0.0001 TO 0.1 WEIGHT PERCENT OF DIISOPROPOYLAMINE; AND D. 0.001 TO 1.0 WEIGHT PERCENT OF EPICHLOROHYDRIN. 